Saturated hydrocarbon-vinyl ether reaction products



United States Patent 2,998,456 SATURATED HYDROCARBON-VINYL ETl-IERREACTION PRODUCTS George J. Benoit, Jr., San Anselmo, Califi, assignorto California Research Corporation, San Francisco, Calif., a corporationof Delaware No Drawing. Filed June 12, I958, Ser. No. 741,460

3 Claims. (Cl. 260-614) This invention pertains to certain particularcompounds and low pour. points are becoming of greater importance aslubricants for equipment such as gas turbine engines, etc.

As set forth in US. Patent 2,748,170, lubricants can be formed byreacting terminally unsaturated olefins with vinyl alkyl ethers, such asto form polymers which are suitable as lubricants. The resultingpolymeric compounds, which have molecular weights from 400 to about 700,have considerable branching within the molecules. Thus, a particulardisadvantage of the lubricant thus prepared is the relatively lowviscosity index obtained.

\ Similarly, as described in U.S. Patent 2,691,646, olefinichydrocarbons may be polymerized with vinyl ethersto form additives forlubricating oil compositions; such ad 'tives being useful for improvingthe viscosity characteristicspf hydrocarbon lubricating oils.

It is a further object of this invention to prepare syntheticlubricating compositions useful as base oils by forming compounds havinghigh viscosity indexes.

In accordance with this invention, it has been discovered that syntheticoils having outstanding characteristics can be prepared by reacting avinyl ether, an allyl ether, or a mixture of such ethers, with asaturated hydrocarbon compound in the presence of a peroxide catalyst.

The products obtained according to this invention have excellentlubricating characteristics such that they are useful as lubricants formachinery, such as gas turbine engines, as base oils for greases, etc.

For simplification in describing this invention, the term ethers as usedherein means vinyl alkyl ethers, divinyl ethers, allyl alkyl ethers anddiallyl ethers. The ethers may be described by the structural formula:

wherein R represents a vinyl or allyl radical, and R is a vinyl radical,an allyl radical, or an alkyl group having from 1 to 5 carbon atoms; Rand R may be the same. For'purposes of this invention, it is preferredthat the ethers have a total of from 3 to 6 carbon atoms.

Examples of ethers of this invention include vinyl ethyl ether, vinylpropyl ether, vinyl butyl ether, vinyl pentyl ether, vinyl hexyl ether,vinyl allyl ether, allyl ethyl ether, allyl butyl ether, allyl pentylether, diallyl ether, etc.

The saturated hydrocarbons with which these ethers are reacted containfrom 10 to 25 carbon atoms; preferably, these saturated hydrocarbons arealiphatic hydrocarbons containing from 14 to carbon atoms. Thesehydrocarbons are exemplified as follows: n-decane, Z-methyldecane,n-dodecane, n-tetradecane, n-hexadecane, n-octadecane,4-rnethylhexadecane, n-eicosane, etc. It is preferable to usestraight-chain saturated hydrocarbons, or hydrocarbons having low degreeof branching. Oils having higher V.I. are obtained by using hydrocarbonshaving low degree of branching.

The catalysts used herein in the preparation of these new synthetic oilsinclude dialkyl peroxides, alkyl hydroperoxides, diacyl peroxides, andmixtures of such peroxides. Preferably, however, the peroxide employedis one of the dialkyl variety such as for example, di-(telrtiary butyl)peroxide, methyl ethyl peroxide, di-(secondary butyl) peroxide, or thelike. Di-(tcrtiary butyl) peroxide is preferred, because it has theadvantage, of commercial availability, and it is relatively stable.

The products formed by reacting the ether with the hydrocarbons shouldcontain, on the average, from about 1 to 5 ether groups per hydrocarbonmolecule. The choice of hydrocarbon employed is determined by thedesired viscosity of the final lubricant. Increasing the number ofattached ether groups beyond about 5 yield oils, the V.I.s

of which are lower than desired. Normally it is preferred to usestraight-chain hydrocarbons having 14 to 20 carbon atoms per moleculereacted with vinyl or allyl ethers having 4 to 6 carbon atoms in whichthe reaction product has about 2 to 3 ether groups attached to thehydrocarbon.

The products useful herein as lubricants are obtained by reacting from 1mol to 5 mols of an ether with from 5 mols to 1 mol of a saturatedhydrocarbon at tempera- I tures ranging from to 200 C., using a catalystsuch as di-(tertiary-butyl) peroxide.

The following examples illustrate the preparation of new synthetic oilsby the reaction ofsaturated hydrocarbons with ethers described herein.

EXAMPLE l.REACTION OF VINYL ETHER WITH CETANE A mixture of 500 grams ofcetane and 10 grams of ditertiary butyl peroxide was placed in astainless steel bomb, which was then capped and flushed with nitrogen.40 grams of vinyl methyl ether was then pumped into the bomb, and theresulting mixture was then heated to C. and maintained at about thattemperature (i.e., 152 C. to 160 C.) for a period of 12 hours, thencooled to room temperature, and the liquid removed. The resultingproduct was fractionally distilled. After the removal of the unreactedcetane, a fraction described hereinbelow as fraction Number 1 wasobtained. Physical properties and analyses of traction No. 1 and thebottoms are set forth hereinbelow in Table 1.

Table 1 (Theory (Theory for One for Two Fraction Vinyl Vinyl No. 1 EtherBottoms Ether Group Groups/ Per Mol- Moleecule) cule) Carbon, percent79. 4 80. 1 77. 3 77.1 Hydrogen, percent 13.9 14.2 12.8 13.5 Oxygen,percent (Difi.). 6.7 5.6 9. 9 9. 3 Molecular Weight 1 267 284. 5 297342. 6 Viscosityat 100 F., cs 5.10 28. 9 at 210 F., cs 1.71 5.32Viscosity Index 129 Fraction No. l and the bottoms were both analyzed byinfrared spectroscopy. The analyses showed strong ether bands atapproximately 8.5 microns in fraction No. l and the bottoms, and astrong band at 13.8 microns (also in fraction No. l and the bottoms)which indicated straight chain hydrocarbons.

EXAMPLE 2.REACTION OF DIALLYL ETHER WITH CETANE A mixture of 300 gramsof cetane, 50 grams of diallyl ether and 3 grams of di-(tertiarybutyl)-peroxide was sees-ass 3 charged to a stainless steel bomb. Thewhole mixture was heated at 135 C. for 12 hours under a blanket ofnitrogen. A liquid product was obtained and fractionated. The unreactedcetane was removed, leaving a bottoms which had the followingcharacteristics:

Viscosity index 153 The oils described herein may be base oils forlubricating compositions used for the lubrication of gas turbineengines, for grease compositions, for hydraulic fluids, etc. In additionto the base oils described herein, the lubricating compositions maycontain oxidation inhibitors, lubricity agents, extreme pressure agents,oiliness agents, corrosion inhibitors, etc.

I claim:

1. A product having the characteristics of an oil of liburicatingviscosity obtained by reacting from 5 to 1 mols of a straight-chainsaturated hydrocarbon containing from 10 to carbon atoms with from 1 to5 mols of an ether at temperatures in the range of C. and 200 C., usinga di(tertiarybutyl) peroxide catalyst, said ether characterized by theformula:

wherein R is an unsaturated radical selected from the group consistingof vinyl and allyl radicals, and R is a radical selected from the groupconsisting of vinyl radical, allyl radical, and alkyl radicalscontaining from 1 to 5 carbon atoms, fractionating the reaction mixtureto recover products having from 1 to 5 ether groups per molecule.

2. A product of claim 1 wherein R is a vinyl radical.

3. The product of claim 1 where R is an allyl radical.

References Cited in the file of this patent UNITED STATES PATENTSPeterson Jan. 1, 1946 Benoit et al. May 29, 1956 5 (1949), pages2891-2893.

1. A PRODUCT HAVING THE CHARACTERISTICS OF AN OIL OF LIBURICATINGVISCOSITY OBTAINED BY REACTING FROM 5 TO 1 MOLS OF A STRAIGHT-CHAINSATURATED HYDROCARBON CONTAINING FROM 10 TO 25 CARBON ATOMS WITH FROM 1TO 5 MOLS OF AN ETHER AT TEMPERATURES IN THE RANGE OF 120*C. AND 200*C.,USING A DI(TERTIARYBUTYL) PEROXIDE CATALYST, SAID ETHER CHARACTERIZED BYTHE FORMULA: